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Discussion papers
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 13 May 2019

Research article | 13 May 2019

Review status
This discussion paper is a preprint. A revision of the manuscript is under review for the journal Atmospheric Chemistry and Physics (ACP).

Kinetics of the OH + NO2 reaction: Rate coefficients (217–333 K, 16–1200 mbar) and fall-off parameters for N2 and O2 bath-gases

Damien Amedro, Arne J. C. Bunkan, Matias Berasategui, and John N. Crowley Damien Amedro et al.
  • Division of Atmospheric Chemistry, Max-Planck-Institut für Chemie, 55128 Mainz, Germany

Abstract. The radical terminating, termolecular reaction between OH and NO2 exerts great influence on the NOy / NOx ratio and O3 formation in the atmosphere. Evaluation panels (IUPAC and NASA) recommend rate coefficients for this reaction that disagree by as much as a factor 1.6 at low temperature and pressure. In this work, the title reaction was studied by pulsed laser photolysis-laser induced fluorescence over the pressure range 16–1200 mbar and temperature 217–333 K in N2 bath-gas, with experiments at 295 K (67–333 mbar) for O2. In-situ measurement of NO2 using two optical-absorption set-ups enabled generation of highly precise, accurate rate coefficients in the fall-off pressure range, appropriate for atmospheric conditions. We found, in agreement with previous work, that O2 bath-gas has a lower collision efficiency than N2 with a relative collision efficiency to N2 of 0.74. Using the widely used Troe-type formulation for termolecular reactions we present a new set of parameters with k0(N2) = 2.6 × 10−30 cm6 molecule−2 s−1, k0(O2) = 2.0 × 10−30 cm6 molecule−2 s−1, m = 3.6, k = 6.3 × 10−11 cm3 molecule−1 s−1, Fc = 0.39 and compare our results to previous studies in N2 and O2 bath-gases.

Damien Amedro et al.
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Damien Amedro et al.
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Publications Copernicus
Short summary
The reaction between the OH radical and nitrogen dioxide play a critical role in controlling abundances of HOx and NOx from the boundary layer to the stratosphere. Uncertainties associated with the rate coefficiet for this reaction lead to uncertainty in model predictions of e.g. the oxidizing capactity of the atmosphere and photochemical ozone production. We present accurate measurements of the rate coefficient over a range of temperatures and pressures.
The reaction between the OH radical and nitrogen dioxide play a critical role in controlling...